Synergistic fungicidal compositions containing 1,2,4-triazole derivatives

ABSTRACT

Synergistic fungicidal compositions comprising ##STR1## in which R 1  is optionally substituted phenyl, 
     R 2  is hydrogen, alkyl or phenyl, 
     R 3  is alkyl, cycloalkyl, phenyl or chlorophenyl, and 
     Y is a keto group or a functional derivative thereof, and at least one member selected from the group consisting of 
     (a) dithiocarbamates, 
     (b) N-polyhaloalkyl-amines or -amides, 
     (c) imidazole and benzimidazole derivatives, 
     (d) optionally nitrated polyhalobenzenes, 
     (e) N-sulphinyl-N&#39;-aryl-hydrazines, and 
     (f) sulphur or alkaline earth metal polysulphides.

The present invention relates to new fungicidal synergistic combinationsof certain 1,2,4-triazole derivatives and certain other fungicidalactive compounds.

It has been disclosed in U.S. Pat. No. 3,912,752 that 1,2,4-triazolederivatives, such as, for example,1-(p-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-2-butanone andthe corresponding 3,4-dichlorophenoxy derivative, exhibit a good actionagainst Ascomycetes and Basidiomycetes, the action against powderymildew fungi deserving special mention, and also against rust diseasesand smut diseases of various crop plants.

The following fungicidal active compounds or groups of active compoundshave also been disclosed:

dithiocarbamates, such as, for example, zinc dimethyldithiocarbamate("ZIRAM") and manganese ethylene-1,2-bis-dithiocarbamate ("MANEB"), aswell as 3-pyrrolidin-1-yl-propyldithiocarbamic acid;

polyhalogenoalkylthio derivatives, such as, for example,N-trichloromethylthio-tetrahydrophthalimide ("CAPTAN"),N-trichloromethylthio-phthalimide ("FOLPET") andN,N-dimethyl-N'-phenyl-N'-fluorodichloromethylthio-sulphamide("DICHLOFLUANID"), and the N'-4-methylphenyl compound analogous to thelatter;

imidazole and benzimidazole derivatives, such as, for example,2-methyl-5-(2',6°-dimethylphenylhydrazono)imidazolenine and2-[2',5'-dimethylpyrazol-1-yl]-1-phenyl-1-isopropylprop-2-yne;

polyhalogenobenzenes, such as, for example, pentachloronitrobenzene;

N-sulphinyl-N'-aryl-hydrazines, such as, for example,N-sulphinyl-N'-(3-chloro-4-trifluoromethyl-phenyl)hydrazine; and

sulphur, and compounds which eliminate sulphur.

The compounds, and groups of compounds, which have been mentioned areknown. As regards dithiocarbamates, polyhalogenoalkylthio derivatives,polyhalogenobenzenes, sulphur and sulphur-eliminating compounds, dataare to be found in R. Wegler "Chemie der Pflanzenschutz- undSchadlingsbekampfungsmitel" ("Chemistry of Plant Protection Agents andPesticides"), volume 2, pages 45 to 150, Heidelberg (1970); regardingthe imidazole and benzimidazole derivatives, see GermanOffenlegungsschriften (German Published Specifications) Nos. 2,129,524,2,130,030 and 2,128,700; regarding the N-sulphinyl-N'-aryl-hydrazines,see German Offenlegungsschrift (German Published Specification) No.2,244,616.

The activity of the previously known active compounds is not fullysatisfactory in all cases if these compounds are employed as individualcomponents.

The present invention now provides a fungicidal composition containingas active ingredients (A) at least one 1,2,4-triazole derivative of thegeneral formula ##STR2## in which R¹ represents phenyl which canoptionally be substituted by halogen, nitro, trifluoromethyl, alkyl withup to 6 carbon atoms, alkoxy with up to 4 carbon atoms or phenyl,

R² represents hydrogen, alkyl with up to 4 carbon atoms or phenyl,

R³ represents alkyl with up to 6 carbon atoms, cycloalkyl with 5 or 6carbon atoms, phenyl or 4-chlorophenyl and

Y represents a group of the formula CO, C═N--OH, C(OH)₂ or CH(OH),

and (B) at least one compound selected from

(a) dithiocarbamates of the general formula ##STR3## in which R⁴ and R⁵each independently represents an optionally substituted aliphaticradical and

X represents hydrogen, one equivalent of a metal atom or the radical(CH₃)₂ N--CS--S,

(b) polyhalogenoalkylthio derivatives of the general formula ##STR4## inwhich R^(b) and R⁷ each independently represents alkyl, aryl,alkylcarbonyl, arylcarbonyl, alkylsulphonyl, arylsulphonyl,amidosulphonyl, alkylamidosulphonyl, dialkylamidosulphonyl,amidocarbonyl, alkylamidocarbonyl or dialkylamidocarbonyl or

R⁶ and R⁷, conjointly with the connecting nitrogen atom, represent anoptionally substituted heterocyclic ring, and

Haloalkyl represents alkyl with up to 2 carbon atoms substituted by 2 to5 halogen atoms,

(c) imidazole and benzimidazole derivatives of the general formula##STR5## in which R⁸ and R⁹ each independently represents hydrogen, anoptionally substituted alkyl, aryl or arylhydrazo radical, or

R⁸ and R⁹ conjointly represent the group

    --CH═CH--CH═CH--

thereby forming a ring system which can optionally be substituted,

R¹⁰ represents hydrogen or an alkyl, aryl, heteroaryl, aralkyl oralkoxycarbonylamino radical, which radical can optionally besubstituted, and

R¹¹ represents hydrogen or an alkyl, aryl, aralkyl, aralkenyl, aralkynylor alkylaminocarbonyl radical, which radical can be substituted or R¹¹can be absent,

(d) polyhalogenobenzenes of the general formula ##STR6## in which Halindependently represents fluorine, chlorine or bromine,

n represents 3, 4, 5 or 6 and

m represents 0, 1, 2 or 3, but n and m together must not be greater than6,

(e) N-sulphinyl-N'-aryl-hydrazines of the general formula ##STR7## inwhich R¹² independently represents methyl, trifluoromethyl, methoxy orhalogen,

T represents trifluoromethyl or trifluoromethoxy and

y represents 0, 1 or 2, and

(f) sulphur or compounds which eliminate sulphur, alone or in admixturewith a solid or liquid or liquefied gaseous diluent or carrier.

Surprisingly, the fungicidal action of the active compound combinationsaccording to the invention is substantially greater than the action ofthe individual components and also than the expected sum of theindividual components. The addition of active compounds from theabove-mentioned groups (a), (b), (c), (d), (e) and (f) to the1,2,4-triazole derivatives of the formula (I) represents an enrichmentof the art.

The 1,2,4-triazole derivatives to be used for the combination accordingto the invention are defined by the general formula (I). In this formulaR¹ represents phenyl, which is preferably substituted by fluorine,chlorine, nitro, trifluoromethyl, methyl, methoxy or phenyl especially4-phenyl, R² preprerably represents hydrogen, R³ preferably representsstraight-chain or branched alkyl with 1 to 4 carbon atoms, phenyl or4-chlorophenyl and Y has the preferred meanings CO or CH(OH). Typicalexamples of known compounds of the formula (I) are1-(p-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-2-butanone andthe corresponding 3,4-dichlorophenoxy compound. The triazoles can beemployed per se or in the form of their salts as described in U.S. Pat.No. 3,912,752.

The dithiocarbamates (group (a)) which can be used as components of themixtures are defined by the formula (II). In this formula, R⁴ preferablyrepresents alkyl with up to 4 carbon atoms, optionally substituted by an--NH--CS--S-- group, by an amino, C₁ -C₄ alkylamino or di-(C₁ -C₄-alkyl)amino group or by a cyclic amine group. R⁵ preferably representshydrogen, methyl or ethyl. X preferably represents thedimethyldithiocarbamoyl radical, hydrogen or one equivalent of a heavymetal atom, such as zinc, manganese, iron or nickel or, if R⁴ is-alkylene-NH--CS--S, two equivalents of the said metals. Typicalexamples of compounds of the formula (II) are: zincN,N-dimethyldithiocarbamate ("ZIRAM"), manganeseethylene-1,2-bis-dithiocarbamate ("MANEB"), zincethylene-1,2-bis-dithiocarbamate ("ZINEB"), zincpropylene-1,2-bis-dithiocarbamate ("PROPINEB"), the co-ordinationcompound formed from manganese ethylene-1,2-bis-dithiocarbamate and zincions ("MANCOZEB"), tetramethylthiuram disulphide ("THIRAM", "TMTD") and3-pyrrolidin-1-yl-dithiocarbamic acid, disclosed in U.S. Pat. No.2,971,884 and German Offenlegungsschrift No. (German PublishedSpecification) No. 2,415,059.

The polyhalogenoalkylthio derivatives (group (b)) which can be used ascomponents of the mixtures are defined by the general formula (III). Inthis formula, the alkyl moieties of R⁶ and R⁷ advantageously each haveup to 4 carbon atoms and the aryl moieties are phenyl, e.g. alkyl and/orhalogeno-phenyl. R⁶ preferably represents amidosulphonyl ordimethylamidosulphonyl and R⁷ preferably represents phenyl, methylphenylor halogenophenyl, or R⁶ and R⁷ conjointly preferably represent theradical ##STR8##

Typical examples of compounds of the general formula (III) are:N-trichloromethylthio-tetrahydrophthalimide ("CAPTAN"),N-trichloromethylthiophthalimide ("FOLPET"),N,N-dimethyl-N'-phenyl-N'-fluorodichloromethylthio-sulfamide("DICHLOFLUANID"),N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide ("CAPTAFOL") andN,N-dimethyl-N'-4-methylphenyl-N'-fluorodichloromethyl-thiosulphamide,disclosed in German Patent Specification No. 1,193,498.

The imidazole and benzimidazole derivatives (group (c)) which can beused as components of the mixtures are generally defined by the formula(IV). In this formula, the alkyl and aryl moieties are advantageously asdefined for R⁶ and R⁷. R⁸ and R⁹ preferably represent hydrogen, alkylwith up to 4 carbon atoms, an optionally C₁₋₄ -alkyl-substitutedphenylhydrazo group or, conjointly, preferably the --CH═CH--CH═CH--. R¹⁰preferably represents hydrogen, alkyl with up to 4 carbon atoms, aheterocyclic five-membered ring with oxygen, sulphur and/or up to twonitrogen atoms as hetero-atoms, which heterocyclic ring can bemethyl-substituted, and also, preferably, alkoxycarbonyl with a total ofup to 5 carbon atoms. R¹¹ preferably represents hydrogen or alkyl,alkenyl or alkynyl, each with up to 8 carbon atoms, and the saidradicals, which can be straight-chain or branched, can also bephenyl-substituted, or R¹¹ preferably represents alkylaminocarbonyl,substituted by a CN group, having a total of 2 to 7 carbon atoms;finally, depending on the position of the double bonds on the ringsystem, the substituent R¹¹ can also be absent. Typical examples ofcompounds of the general formula (IV) are:2-methyl-5-(2',6'-dimethylphenylhydrazono)-imidazolenine,2-[2',5'-dimethylpyrazol-1'-yl]-benzimidazole and1-[imidazol-1'-yl]-1-phenyl-1-isopropyl-prop-2-yne from GermanOffenlegungsschriften (German Published Specifications) Nos. 2,129,524,2,130,030 and 2,128,700,1-(N-butylcarbamoyl)-2-(methoxycarbonylamino)-benzimidazole ("BENOMYL").2-(methoxy-carbonylamino)-benzimidazole ("BCM", "CARBENDAZIM") from U.S.Pat. No. 3,657,443, 2-(2'-benzimidazole ("THIABENDAZOL") and1-(5-cyanopentyl-carbamoyl)-2-(methoxycarbonylamino)-benzimidazole("CYPENDAZOL") from German Offenlegungsschrift (German PublishedSpecification) No. 1,812,005; and the remaining compounds are generallyknown and are to be found in standard works.

In place of those above-mentioned compounds of the group (c) which arederivatives of 2-aminobenzimidazole, it is also possible to employcompounds which are converted to 2-aminobenzimidazole derivatives undersuitable conditions. Here there should be mentioned1,1'-o-phenylene-bis-(3,3'-ethoxycarbonylthiourea)("THIOPHANATE") andthe corresponding methoxycarbonyl compound, as well as yet furtherderivatives of o-phenylenediamine.

The polyhalogenobenzenes (group (d)) which can be used as compounds ofthe mixtures are defined by the general formula (V). In this formula,Hal preferably represents chlorine, n preferably represents 5 or 6 and mpreferably represents 0 or 1, but n and m together must not be greaterthan 6. Compounds which may be mentioned as having been known world-widefor a long time are hexachlorobenzene and pentachloronitrobenzene("QUINTOZEN").

In place of the above-mentioned compounds of the group (d) other activecompounds, which contain at least 2 chlorine atoms on the nucleus, canalso be used. Here there should be mentioned:tetrachloroisophthalodinitrile ("CHLOROTHALONIL"),1,4-dichloro-2,5-dimethoxybenzene ("CHLORONEB") and4,5,6,7-tetrachlorophthalide from U.S. Pat. No. 3,663,704.

The N-sulphinyl-N'-aryl-hydrazines (group (e)) which can be used ascomponents of the mixtures are defined by the general formula (VI). Inthis formula, R¹² preferably represents chlorine and T preferablyrepresents trifluoromethyl. An example to be mentioned isN-sulphinyl-N'-(3-chloro-4-trifluoromethylphenyl)-hydrazine. Thecompounds are known (see German Offenlegungsschrift (German PublishedSpecification) No. 2,244,616).

Sulphur, or the sulphur-eliminating compounds (group (f)) which can beused as compounds of the mixtures have been known for a long time asfungicidally active materials. Sulphur-eliminating compounds which areused preferentially are the alkaline earth metal polysulphides, such ascalcium polysulphide and barium polysulphide; the last-mentionedcompounds, again, are generally known.

Instead of the preferred components of the mixtures, from groups (a),(b), (c), (d), (e) and (f), which according to the present invention areto be used in a mixture with the 1,2,4-triazole derivatives of theformula (I), it is also possible to use, as partners for the1,2,4-triazole derivatives in the mixture: azo compounds, such as thesodium salt of p-dimethylaminophenyl-diazosulphonic acid("FENAMINOSULF") and quinonoxime-benzoylhydrazone ("BENQUINOX");guanidine derivatives, such as n-dodecylguanidine acetate ("DODINE");triazino derivatives, such as2,4-dichloro-6-(o-chloroanilino)-1,3,5-triazine ("ANILAZIN");bis-trifluoromethylimino derivatives, such as2-methylimino-3-(4'-chlorophenyl)-4,5-bis-(trifluoromethylimino)-thiazolidine;inorganic metal salts, such as, for example, inorganic copper compounds;metal-organic compounds, such as, for example, organic tin compounds andorganic mercury compounds; organo-phosphorus derivatives, such as, forexample, dithiolphosphoric acid O-ethyl-S,S-diphenyl ester("EDIFENPHOS"), thiolphosphoric acid O,O-diethyl-S-benzyl ester,dithiolphosphoric acid O-butyl-S-ethyl-S-benzyl ester andbenzenethiolphosphoric acid O-methyl-S-benzyl ester; oxathiines, such as2,3-dihydro-6-methyl-1,4-oxathiine-5-carboxylic acid anilide and thecyclic sulphone derived from the latter compound; and anthraquinonederivatives, such as 2,3-dicyano-1,4-dithia-anthraquinone.

The active compounds mentioned in the preceding paragraph can also beadded as a further component (for example as a third component) to amixture of a 1,2,4-triazole derivative and an active compound from thegroups (a) to (b).

The weight ratio of the groups of active compounds in the activecompound combinations can vary within relatively wide ranges. Ingeneral, 0.1 to 500 parts by weight of active compound from activecompound classes (a) to (f), preferably 0.2 to 200 and especially about0.3 to 3.5 parts by weight from the latter classes, are present per partby weight of 1,2,4-triazole derivative.

The active compound combinations according to the invention exhibit apowerful fungitoxic action. They do not damage crop plants in theconcentrations required for combating fungi and have a low toxicity towarm-blooded animals. For these reasons, they are suitable for use asplant protection agents for combating fungi and bacteria. Fungitoxicagent are employed in plant protection for combatingPlasmodiophoromycetes, Chytridiomycetes, Oomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

The active compound combinations according to the invention have a verybroad spectrum of action and can be used against parasitic fungi whichinfect aboveground parts of plants or which attack the plants throughthe soil, and against seed-borne pathogens. Such active compoundcombinations are of particular practical importance as seed dressingsused against phytopathogenic fungi which are borne with the seed oroccur in the soil and infest the crop plants from there. What isconcerned are seedling diseases, root rots and diseases of stalks,stems, leaves, blossoms, fruit and seeds which are caused, inparticular, by species of Tilletia, Urocystis, Ustilago, Septoria,Typhula, Rhynchosporium, Helminthosporium and Fusarium. As a result ofthe systemic action of one component of the mixture, the plants are alsofrequently even protected for a long time after dressing, againstpathogens which can attack various parts of the shoot, for exampleErysiphe graminis and species of Puccinia. The active compoundcombinations can also be employed as soil treatment agents againstphytopathogenic fungi and act against root rots and tracheomycoses whichare caused, for example, by pathogens of the genera Pythium,Verticillium, Phialophora, Rhizoctonia, Fusarium and Thielaviopsis.

However, the active compound combinations according to the inventionalso exhibit an excellent action, when applied directly to theabove-ground parts of plants, against pathogens present on various cropplants, such a powdery mildew fungi (species of Erysiphe, Uncinula,Sphaerotheca and Podosphaera, and Leveillua taurica), rust fungi,species of Venturia, species of Cercospora, species of Alternaria,species of Botrytis, species of Phytophthora, species of Peronospora,Pyricularia oryzae and Pellucularia sasakii.

The active materials according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents, carriers or extenders ofthe type usable in conventional pesticide formulations or compositions,e.g. conventional pesticide dispersible carrier vehicles such as gases,solutions, emulsions, suspensions, emulsifiable concentrates, spraypowders, pastes, soluble powders, dusting agents, granules, etc. Theseare prepared in known manner, for instance by extending the activecompounds with conventional pesticide dispersible liquid diluentcarriers and/or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticide surface-activeagents, including emulsifying agents and/or dispersing agents, whereby,for example, in the case where water is used as diluent, organicsolvents may be added as auxiliary solvents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: aerosol propellants which are gaseous at normal temperaturesand pressures, such as Freon; inert dispersible liquid diluent carriers,including inert organic solvents, such as aromatic hydrocarbons (e.g.benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated,especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes,etc.), cycloalkanes, (e.g. cyclohexane, etc.), paraffins (e.g. petroleumor mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g.methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol,ethanol, propanol, butanol, glycol, etc.) as well as ethers and estersthereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine,etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethylsulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethylketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; aswell as inert dispersible finely divided solid carriers, such as groundnatural minerals (e.g. kaolins, clays, alumina, silca, chalk, i.e.calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.)and ground synthetic minerals (e.g highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose; emulsifying agents (e.g.polyethylene oxide esters of fatty acids, polyethylene oxide ethers offatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates,albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers,magnesium stearate, sodium oleate, etc.); and/or dispersing agents, suchas lignin, sulfite waste liquors, methyl cellulose, etc.

Such active materials may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other fungicides, orinsecticides, acaricides, nematocides, bactericides, rodenticides,herbicides, fertilizers, growth-regulating agents, etc., if desired, orin the form of particular dosage preparations for specific applicationmade therefrom, such as solutions, emulsions, suspensions, powders,pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active materialsis present in an amount substantially between about 0.1-95% by weight,and preferably 0.5-90% by weight, of the mixture, whereas carriercomposition mixtures suitable for direct application or fieldapplication generally contemplate those in which the active material ispresent in an amount substantially between about 0.0001-10%, preferably0.01-1%, by weight of the mixture. Thus, the present inventioncontemplates overall compositions which comprise mixtures of aconventional dispersible carrier vehicle such as (1) a dispersible inertfinely divided carrier solid, and/or (2) a dispersible carrier liquidsuch as an inert organic solvent and/or water, preferably including asurface-active effective amount of a carrier vehicle assistant, e.g. asurface-active agent, such as an emulsifying agent and/or a dispersingagent, and an amount of the active material which is effective for thepurpose in question and which is generally between about 0.0001-95%, andpreferably 0.01-95%, by weight of the mixture.

The active materials can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 15 to 1000 g/hectare, preferably 40to 600 g/hectare, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of the activematerial or even the 100% active substance alone, e.g. about 20-100% byweight of the active material.

Especially when used as leaf fungicides, the active compoundconcentrations in the use forms can be varied within a fairly widerange. They are, in general, from 0.5 to 0.0005 percent by weight andpreferably form 0.2 to 0.001 percent.

For the treatment of seed, amounts of active compound of 0.01 to 50 gper kilogram of seed, preferably 0.1 to 5 g, are generally required.

For the treatment of soil, amounts of active compound of 1 to 1,000 gper cubic meter of soil, preferably 10 to 200 g, are generally required.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. fungi, which comprisesapplying to at least one of correspondingly (a) such fungi, and (b) thecorresponding habitat thereof, i.e. the locus to be protected, e.g. to agrowing crop, to an area where a crop is to be grown or to a domesticanimal, a correspondingly combative or toxic amount, i.e. a fungicidallyeffective amount, of the particular active compound of the inventionalone or together with a carrier vehicle as noted above. The instantformulations or compositions are applied in the usual manner, forinstance by spraying, atomizing, vaporizing, scattering, dusting,watering, squirting, sprinkling, pouring, fumigating, dry dressing,moist dressing, wet dressing, slurry dressing, encrusting, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particularnew compounds of the present invention are illustrated, withoutlimitation, by the following examples:

EXAMPLE 1 Erysiphe test (cucumbers)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

Water: 95 parts by weight

The amount of the active compound required for the desired concentrationof active compound in the spray liquid was mixed with the stated amountof water containing the stated additions.

Young cucumber plants with about three foliage leaves were sprayed withthe spray liquid until dripping wet. The cucumber plants remained in agreenhouse for 24 hours to dry. They were then, for the purpose ofinoculation, dusted with conidia of the fungus Erysiphe cichoracearum.The plants were subsequently placed in a greenhouse at 23°-24° C. and ata relative atmospheric humidity of about 75%.

After 12 days, the infection of the cucumber plants was determined. Theassessment data were converted to percent infection. 0% means noinfection; 100% that the plants were totally infected.

The active compounds, the concentrations of the active compounds and theresults can be seen from the following table.

                                      TABLE 1                                     __________________________________________________________________________    Erysiphe test (cucumbers)/protective                                          __________________________________________________________________________                         Infection in % at                                                             an active compound concentration of                      Active compound      0.01%                                                                             0.005%                                                                            0.000125%                                                                           0.000062%                                  __________________________________________________________________________    Known individual active compounds:                                             ##STR9##                    25    41                                          ##STR10##           87  100                                                   ##STR11##           100 100                                                  Sulphur (4)          66  100                                                  __________________________________________________________________________    Active compound                                                               __________________________________________________________________________    Mixtures according to the invention:                                          Mixture of (1) + (2)                                                          Mixing ratio           1:40  1:80  1:160                                      Concentration of (1)   0.000125%                                                                           0.000062%                                                                           0.000062%                                  Concentration of (2)   0.005%                                                                              0.005%                                                                              0.01%                                      Infection              12    25    29                                         Mixture of (1) + (3)                                                          Mixing ratio                 1:80  1:160                                      Concentration of (1)         0.000062%                                                                           0.000062%                                  Concentration of (3)         0.005%                                                                              0.01%                                      Infection                    25    34                                         Mixture of (1) + (4)                                                          Mixing ratio                 1:80  1:160                                      Concentration of (1)         0.000062%                                                                           0.000062%                                  Concentration of (4)         0.005%                                                                              0.01%                                      Infection                    29    25                                         __________________________________________________________________________

EXAMPLE 2 Fusicladium test (apple)/(protective)

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

Water: 95 parts by weight

The amount of active compound required for the desired concentration ofthe active compound in the spray liquid was mixed with the stated amountof solvent, and the concentrate was diluted with the stated amount ofwater which contained the stated additions.

Young apple seedlings in the 4-6 leaf stage were sprayed with the sprayliquid until dripping wet. The plants remained in a greenhouse for 24hours at 20° C. and at a relative atmospheric humidity of 70%. They werethen inoculated with an aqueous conidium suspension of the apple scabcausative organism (Fusicladium dendriticum) and incubated for 18 hoursin a humidity chamber at 18°-20° C. and at a relative atmopsherichumidity of 100%.

The plants were then brought into a greenhouse for 14 days.

15 days after inoculation, the infection of the seedlings wasdetermined. The assessment data were converted to percent infection. 0%means no infection; 100% means that the plants were totally infected.

The active compounds, the concentrations of the active compounds and theresults can be seen from the following table:

                  TABLE 2                                                         ______________________________________                                        Fusicladium test (apple)/(protective)                                                                Infection in % at                                                             an active compound                                                            concentration                                          Active compound        of 0.00062%                                            ______________________________________                                        Known individual active                                                       compounds:                                                                     ##STR12##             17                                                      ##STR13##             30                                                      ##STR14##             16                                                     Mixtures according to the invention:                                          Mixture of (1) + (5)                                                          Mixing ratio           1:1                                                    Concentration of (1)   0.00062%                                               Concentration of (5)   0.00062%                                               Infection                12                                                   Mixture of (1) + (6)                                                          Mixing ratio           1:1                                                    Concentration of (1)   0.00062%                                               Concentration of (6)   0.00062%                                               Infection                 1                                                   ______________________________________                                    

EXAMPLE 3 Seed dressing test/bunt of wheat (seed-borne mycosis)

To produce a suitable dry dressing, the active compound was extendedwith a mixture of equal parts by weight of talc and kieselguhr to give afinely powdered mixture with the desired concentration of the activecompound.

Wheat seed was contaminated with 5 g of the chlamydospores of Tilletiacaries per kg of seed. To apply the dressing, the seed was shaken withthe dressing in a closed glass flask. The seed, on moist loam under acover of a layer of muslin and 2 cm of moderately moist compost soil,was exposed to optimum germination conditions for the spores for 101days at 10° C. in a refrigerator.

The germination of the spores on the wheat grains, each of which wascontaminated with about 100,000 spores, was subsequently determinedmicroscopically. The smaller the number of spores which had germinated,the more effective was the active compound.

The active compounds, the amounts of the active compounds used, and thepercentage spore germination can be seen from the following table.

                                      TABLE 3                                     __________________________________________________________________________    Seed dressing test/bunt of wheat                                                                   Amount of active compound                                Active compounds     used, in g/dt* of seed                                                                      Spore germination                          __________________________________________________________________________    no dressing          --            >10%                                       Known individual active compounds:                                             ##STR15##           100 50 25     >10% >10% >10%                              ##STR16##            30           slight                                     Pentachloronitrobenzene (8)                                                                         60           slight                                                           30           slight                                     [(CH.sub.3).sub.2 NCSS].sub.2 Zn (9)                                                               160           slight                                     Mixtures according to the invention:                                          (1) + (7)             25 + 30      none                                       (1) + (8)             25 + 25      none                                       (1) + (9)             50 + 160     none                                       __________________________________________________________________________     *dt = decitonne = 100 kg                                                 

EXAMPLE 4 Seed dressing test/bunt of wheat/field trial (seed-bornemycosis)

To produce a suitable dry dressing, the active compound was extendedwith a mixture of equal parts by weight of talc and kieselguhr to give afinely powdered mixture with the desired concentration of the activecompound.

Dressing was effected in 4 individual portions each of 100 g. which weresown onto 4 plots of size 5 m². The percentages of infection which arequoted hereinafter were obtained by completely counting all diseasedears on the individual plots and estimating the total number of all earsfom counting a few plots in which the growth was apparently equallydense.

For testing the action against bunt of wheat (Tilletia caries), winterwheat (certified seed), which had beforehand been contaminated with 2 gof chlamydospores per kg of seed, was used.

Dressing: beginning of October

Sowing: 10th to 20th October

Evaluation: end of June to middle of July

The percentage of diseased ears were based in each case on about 2,000ears per plot=a total of about 8,000 cars per experimental entry.

The active compounds, the amounts of active compound used and the numberof diseased ears can be seen from the table which follows:

                                      TABLE 4                                     __________________________________________________________________________    Seed dressing test/bunt of wheat/field trial                                                                      Number of ears infected                                         Amount of active compound                                                                   with bunt, in % of the                    Active compounds      used in g/dt of seed                                                                        total number of ears                      __________________________________________________________________________    without dressing      --            52.82                                     Known individual active compounds                                              ##STR17##            50            0.67                                       ##STR18##            60            2.39                                       ##STR19##            40            0.34                                       ##STR20##            100           0.56                                      Known individual active compounds:                                            Pentachloronitrobenzene (8)                                                                         20            0.11                                       ##STR21##            60            0.76                                      Mixtures according to the invention:                                          (1) + (7)             50 + 30       0.12                                      (1) + (10)            50 + 20       0.02                                                            50 + 40       0.00                                      (1) + (11)             50 + 100     0.00                                      (1) + (8)             50 + 20       0.02                                      (1) + (12)            50 + 30       0.09                                                            50 + 60       0.01                                      __________________________________________________________________________

EXAMPLE 5 Seed dressing test/stripe disease of barley (seed-bornemycosis)

To produce a suitable dry dressing, the active compound was extendedwith a mixture of equal parts by weight of talc and kieselguhr to give afinely powdered mixture with the desired concentration of activecompound.

To apply the dressing, barley seed, which was naturally infected byDrechslera graminea (previously Helminthosporium gramineum), was shakenwith the dressing in a closed glass flask. The seed, on moist filterpaper discs in closed Petri dishes, was exposed to a temperature of 4°C. for 10 days in a refrigerator. The germination of the barley, andpossibly also of the fungus spores, was thereby initiated. Two batchesof 50 grains of the pregerminated barley were subsequently sown 2 cmdeep in Fruhstorfer standard soil and cultivated in a greenhouse attemperatures of about 18° C. in seed boxes which were exposed to lightfor 16 hours daily. The typical symptoms of the stripe disese developedwithin 3 to 4 weeks.

After this time, the number of diseased plants was determined as apercentage of the total number of emerged plants. The fewer plants werediseased, the more effective was the active compound.

The active compounds, the amounts of the active compounds used and thenumber of diseased plants can be seen from the following table:

                                      TABLE 5                                     __________________________________________________________________________    Seed dressing test/stripe disease of barley                                                                     Number of plants with stripe                                     Amount of active com-                                                                      disease in % of the total                   Active compound      pound used in g/dt of seed                                                                 number of emerged plants                    __________________________________________________________________________    no dressing          --           55.7                                        Known individual active compounds:                                             ##STR22##            50          20.0                                         ##STR23##            40           2.1                                         ##STR24##            30 20        4.1 6.3                                     ##STR25##            40           2.0                                         ##STR26##           100           9.1                                        Mixtures according to the invention:                                          (1) + (13)            50 + 40      0.0                                        (1) + (14)            50 + 30      0.0                                                              50 + 15      0.0                                        (1) + (10)            50 + 40      0.0                                        (1) + (11)            50 + 100     2.1                                        __________________________________________________________________________

EXAMPLE 6 Seed dressing test/stripe disease of barley/field trial(seed-borne mycosis)

To produce a suitable dry dressing, the active compound was extendedwith a mixture of equal parts by weight of talc and kieselguhr to give afinely powdered mixture with the desired concentration of the activecompound.

Dressing was effected in 4 individual portions each of 100 g, which weresown onto 4 plots of size 5 m². The percentages of infection which arequoted hereinafter were obtained by completely counting all diseasedstems on the individual plots and estimating the total number of allstems from counting a few plots in which the growth was apparentlyequally dense.

To test the action against stripe disease of barley, summer barley wasused, which was naturally infected with Drechslera graminea (previouslyreferred to as Helminthosporium gramineum).

Dressing: middle of February

Sowing: end of February

Evaluation: beginning of June

The percentages of diseased stems were based in each case on about 2,000stems per plot=a total of about 8,000 stems per experimental entry.

The active compounds, the amounts of active compound used and the numberof diseased stems can be seen from the table which follows:

                                      TABLE 6                                     __________________________________________________________________________    Seed dressing test/stripe disease of barley/field trial                                                            Number of stems with stripe                                     Amount of active compound                                                                   disease in % of the total                Active compound        used in g/dt of seed                                                                        number of stems                          __________________________________________________________________________    no dressing            --            59.29                                    Known individual active compounds:                                             ##STR27##             50            14.51                                     ##STR28##             30            2.92                                      ##STR29##             100           5.81                                     Known individual active compounds:                                             ##STR30##             60            0.88                                     [(CH.sub.3).sub.2 NCSS].sub.2 Zn (9)                                                                 160           26.25                                    Mixtures according to the invention:                                          (1) + (14)             50 + 30       0.47                                     (1) + (11)              50 + 100     2.48                                     (1) + (12)             50 + 30       0.45                                                            50 + 60       0.04                                     (1) + (9)               50 + 160     10.47                                    __________________________________________________________________________

EXAMPLE 7 Seed dressing test/Septoria nodorum on wheat (seed-bornemycosis)

To produce a suitable dry dressing, the active compound was extendedwith a mixture of equal parts by weight of talc and kieselguhr to give afinely powdered mixture with the desired concentration of activecompound.

To apply the dressing, wheat seed, which was naturally infected bySeptoria nodorum, was shaken with the dressing in a closed glass bottle.2 batches of 100 grains of the seed were sown 1 cm deep in quartz sandin seed boxes and were cultivated in a greenhouse at temperatures of 15°C. The typical symptoms of Septoria nodorum developed over the course of3 weeks.

After this time, the number of diseased plants was determined as apercentage of the total number of emerged plants. The fewer plants werediseased, the more effective was the active compound.

The active compounds, the amounts of the active compound used and thenumber of diseased plants can be seen from the following table:

                                      TABLE 7                                     __________________________________________________________________________    Seed dressing test/Septoria nodorum on wheat                                                                    Number of diseased plants                                        Amount of active compound                                                                  in % of the total number                    Active compound      used in g/dt of seed                                                                       of emerged plants                           __________________________________________________________________________    no dressing          --           95.0                                        Known individual active compounds                                              ##STR31##           75           12.4                                         ##STR32##           80           35.8                                        Mixture according to the invention:                                           (1) + (11)           75 + 80      6.2                                         __________________________________________________________________________

EXAMPLE 8 Seed dressing test/bunt of wheat (seed-borne mycosis)

To produce a suitable dry dressing, the particular active compound isextended with a mixture of equal parts by weight of talc and kieselguhrto provide a finely powdered mixture with the desired finalconcentration of such active compound.

Wheat seed is contaminated with 5 g of the chlamydospores of Tilletiacaries per kg of seed. To apply the given dressing, the seed is shakenwith such dressing in a closed glass flask. The seed, on moist loamunder a cover of a layer of muslin and 2 cm of moderatedly moist compostsoil is exposed to optimum germination conditions for the spores of 10days at 10° C. in a refrigerator.

The germination of the spores on the wheat grains, each of which iscontaminated with about 100,000 spores, is subsequently determinedmicroscopically. The smaller the number of spores which have germinated,the more effective is given active compound.

The particular active compounds tested, their concentrations in thedressing, the amounts of dressing used and the percentage sporegermination obtained can be seen from the following Table 8.

                  TABLE 8                                                         ______________________________________                                        Seed dressing test/bunt of wheat                                                                     Amount    Spore                                                               of active ger-                                                                compounds mina-                                        Active compound        in g/dt*  tion                                         ______________________________________                                        no dressing                      >10                                          Known individual                                                              active compounds:                                                              ##STR33##             25        >10                                           ##STR34##             25        me- dium                                     Mixtures according                                                            to the invention:                                                             (1) + ANILAZIN         25 + 25   weak                                         ______________________________________                                         *dt = deciton = 100 kg                                                   

EXAMPLE 9 Shoot treatment test/cereal rust/protective (leaf-destroyingmycosis)

To produce a suitable preparation of active compound, 0.25 part byweight of active compound was taken up in 25 part by weight ofdimethylformamide and 0.06 part by weight of Emulsifier W, and 975 partsby weight of water were added. The concentrate was diluted with water tothe desired final concentration of the spray liquor.

To test the protective activity, young wheat plants of the MichiganAmber variety, having one leaf, were inoculated with a uredosporesuspension of

Puccinia recondita in 0.1% strength aqueous agar. After the sporesuspension had dried off, the wheat plants were sprayed with thepreparation of active compound until dew-moist and were placed in agreenhouse to incubate for 24 hours at about 20° C. and 100% atmospherichumidity.

After leaving the plants for 10 days at a temperature of 20° C. and80-90% atmospheric humidity, the occurrence of rust pustules on theplants was evaluated. The degree of infection was expressed in percentof the infection of the untreated control plants. 0% denotes noinfection and 100% denotes the same degree of infection as in the caseof the untreated control. The lower the infection with rust, the moreactive is the compound being tested.

The active compounds, active compound concentrations in the spray liquorand degrees of infection can be seen from the Table 9 which follows:

                  TABLE 9                                                         ______________________________________                                        Shoot treatment test/cereal rust/protective                                                       Active                                                                        compound                                                                      concentration                                                                            Infection in                                                       in the spray                                                                             % of the                                                           liquor, in %                                                                             untreated                                      Active compounds    by weight  control                                        ______________________________________                                        Untreated           --         100.0                                          Known individual                                                              active compounds                                                               ##STR35##          0.005      50.0                                            ##STR36##          0.08       12.5                                           Mixtures according to the invention                                           (1) + ANILAZIN      0.005 + 0.08                                                                             0.0                                            ______________________________________                                    

A mixture consisting of 1,2,4-triazole derivative, especially the1-(p-chlorophenoxy)-3,3-dimethyl-1-(1,2,4triazol-1-yl)-2-butanone andthe triazino derivative 2,4-dichloro-6-(o-chloroanilino)-1,3,5-triazine("ANILAZIN") is suitable for combating diseases on the leaves and theears of cereal crops, preferably in weight ratios of 12 to 20 parts byweight of ANILAZIN to one part by weight of 1,2,4-triazole derivative.This composition is effective against powdery mildew (Erisyphegraminis), rost diseases (Puccinia striiformis and Puccinia recondita)and Rhynchosphorium species, and also against important Septoria species(Septoria nodorum, Septoria tritici). Further, the composition issuitable for the simultaneous control of coffee rost disease (Hemileiavastatrix) and the coffee berry disease (Colletotrichum coffeanum),preferably in weight ratios from 1.5 to 12 parts by weight of ANILAZINto one part by weight of 1,2,4-triazole derivative.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. A fungicidal composition containing as activeingredients (A) a 1,2,4-triazole derivative of the formula ##STR37## inwhich R¹ is phenyl, or phenyl substituted by halogen, nitro,trifluoromethyl, alkyl with up to 6 carbon atoms, alkoxy with up to 4carbon atoms or phenyl.R² is hydrogen, alkyl with up to 4 carbon atomsor phenyl, R³ is alkyl with up to 6 carbon atoms, cycloalkyl with 5 or 6carbon atoms, phenyl or 4-chlorophenyl, and,Y is CO, C(OH)₂ or (CH(OH).and (B) 0.2 to 200 times the weight of (A) of a compound selected fromthe group consisting of (a) dithiocarbamates of the formula ##STR38## inwhich R⁴ is alkyl with 1 to 4 carbon atoms which is optionallysubstituted by an --NH--CS--S-- group, by an amino, C₁ -C₄ alkylamino ordi-(C₁ -C₄ -alkyl) amino,R⁵ is hydrogen, methyl or ethyl, and X ishydrogen, one equivalent of a metal atom or the radical (CH₃)₂ N--CS--S,(b) polyhalogenoalkylthio derivatives of the formula ##STR39## in whichR⁶ is amidosulphonyl or dmethylamidosulphonyl,R⁷ is phenyl, methylphenylor halogenophenyl, or R⁶ and R⁷ conjointly represent the radical##STR40## (c) imidazole and benzimidazole derivatives selected from thegroup consisting of ##STR41## (d) sulphur or an alkaline earth metalpolysulphide.
 2. A composition according to claim .[.1.]. .Iadd.16,.Iaddend.(A) is a 1,2,4-triazole derivative in whichR¹ is phenyloptionally substituted by fluorine, chlorine, nitro, trifluoromethyl,methyl, methoxy or phenyl, R² is hydrogen, R³ is alkyl with 1 to 4carbon atoms, phenyl or 4-chlorophenyl, and Y is a CO or CH(OH) group,and (B) is(a) a dithiocarbamate of the formula ##STR42## in which R⁴ isalkyl with 1 to 4 carbon atoms which is optionally substituted by an--NH--CS--S-- group, by an amino, C₁ -C₄ -alkylamino or di-(C₁ -C₄-alkyl)amino, R⁵ is hydrogen, methyl or ethyl, and X is (CH₃)₂ N--CS--S,hydrogen or one equivalent of a heavy metal, whereby a furtherequivalent of a heavy metal satisfies the remaining valency when R⁴ isalkyl substituted by --NH--CS--S--.
 3. A fungicidal compositionaccording to claim 2, containing as active ingredients (A) the compoundof the formula ##STR43## and (B) at least one compound selected from thegroup consisting of elementary sulfur, ##STR44##
 4. A fungicidalcomposition according to claim 3, wherein (B) is sulfur.
 5. A fungicidalcomposition according to claim 3, wherein (B) is ##STR45##
 6. Afungicidal composition according to claim 3, wherein (B) is ##STR46## 7.A fungicidal composition according to claim 3, wherein (B) is ##STR47##8. A fungicidal composition according to claim 3, wherein (B) is##STR48##
 9. A fungicidal composition according to claim 3, wherein (B)is

    [(CH.sub.3).sub.2 N--CS--S--].sub.2 Zn


10. A fungicidal composition according to claim 3, wherein (B) is##STR49##
 11. A fungicidal composition according to claim 3, wherein (B)is ##STR50##
 12. A method of combating fungi which comprises applying tothe fungi, or to a habitat thereof, a fungicidally effective, amount ofa composition according to claim .[.1.]. .Iadd.16.Iaddend..
 13. A methodof combating fungi which comprises applying to the fungi, or to ahabitat thereof, a fungicidally effective amount of a compositionaccording to claim
 3. 14. The method according to claim 12, in which thecomposition is applied to soil in a total amount of about 1 g to 100 gof active material per cubic meter of soil.
 15. The method according toclaim 12, in which the composition is applied to seed in a total amountof about 0.01 g to 50 g of active material per kg of seed. .Iadd.
 16. Afungicidal composition containing as active ingredients (A) a1,2,4-triazole derivative of the formula ##STR51##.Iaddend. in whichR¹is phenyl, or phenyl substituted by halogen, nitro, trifluoromethyl,alkyl with up to 6 carbon atoms, alkoxy with up to 4 carbon atoms orphenyl; R² is hydrogen, alkyl with up to 4 carbon atoms or phenyl; R³ isalkyl with up to 6 carbon atoms, cycloalkyl with 5 or 6 carbon atoms,phenyl or 4-chlorophenyl, and, Y is CO, C(OH)₂ or CH(OH).and (B) 0.2 to200 times the weight of (A) of a compound selected from the groupconsisting of (a) dithiocarbamates of the formula ##STR52## in which R⁴is alkyl with 1 to 4 carbon atoms which is optionally substituted by an--NH--CS--S-- group, by an amino, C₁ -C₄ alkylamino or di-(C₁ -C₄-alkyl) amino group R⁵ is hydrogen, methyl or ethyl, and X is hydrogen,one equivalent of a metal atom or the radical (CH₃)₂ N--CS--S, (b)polyhalogenoalkylthio derivatives of the formula ##STR53## in which R⁶is amidosulphonyl or dimethylamidosulphonyl, R⁷ is phenyl, methylphenylor halogenophenyl, or R⁶ and R⁷ conjointly represent the radical##STR54## (c) imidazole and benzimidazole derivatives selected from thegroup consisting of ##STR55## (d) sulphur or an alkaline earth metalpolysulphide. .Iadd.
 17. A composition according to claim 16, wherein(B)is ##STR56##.Iaddend. .Iadd.
 18. A composition according to claim 17,wherein(A) is ##STR57##.Iaddend. .Iadd.
 19. A method of combating fungiwhich comprises applying to the fungi, or to a habitat thereof, afungicidally effective amount of a composition according to claim16..Iaddend. .Iadd.20. A method of combating fungi which comprisesapplying to the fungi, or to a habitat thereof, a fungicidally effectiveamount of a composition according to claim
 17. .Iaddend. .Iadd.21. Amethod of combating fungi which comprises applying to the fungi, or to ahabitat thereof, a fungicidally effective amount of a compositionaccording to claim 18..Iaddend.